skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation

Abstract

Metal organic frameworks (MOFs) have emerged as a novel platform offering new promise for photocatalytic applications. In this work, we report a mixed-node MOF (MOF-74) based on earth-abundant metals (i.e., Co and Fe) as highly active and robust photocatalysts for visible light-driven H2 generation. Using in situ X-ray absorption spectroscopy which allows us to selectively probe the individual metal node in MOFs, we unambiguously identified the catalytic active sites and captured the key intermediate species under the standard catalytic conditions. We show that both Co and Fe centers in MOF-74 are the reversible active sites, and the accumulation of their reduced states is responsible for the observed induction period for H2 generation. Moreover, we captured the key intermediate species formed when the reaction reaches equilibrium, which is featured by an elongated Co–O bond at the Co center and a more distorted octahedral geometry at the Fe center with respect to their original geometry. These results not only demonstrate the potential of MOF-74 as a single site catalyst for H2 generation but also provide new insight into the catalytic mechanism for further development.

Authors:
 [1];  [2];  [2];  [3];  [2];  [2]; ORCiD logo [4];  [3]; ORCiD logo [2]
  1. Wuyi Univ., Jiangmen (China); Marquette Univ., Milwaukee, WI (United States)
  2. Marquette Univ., Milwaukee, WI (United States)
  3. Wuyi Univ., Jiangmen (China)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Petroleum Research Fund (PRF); Wuyi University
OSTI Identifier:
1595943
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 2; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhou, Yixuan, Hu, Wenhui, Yang, Sizhuo, Zhang, Yunbo, Nyakuchena, James, Duisenova, Korlan, Lee, Sungsik, Fan, Donghua, and Huang, Jier. Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcc.9b09634.
Zhou, Yixuan, Hu, Wenhui, Yang, Sizhuo, Zhang, Yunbo, Nyakuchena, James, Duisenova, Korlan, Lee, Sungsik, Fan, Donghua, & Huang, Jier. Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation. United States. https://doi.org/10.1021/acs.jpcc.9b09634
Zhou, Yixuan, Hu, Wenhui, Yang, Sizhuo, Zhang, Yunbo, Nyakuchena, James, Duisenova, Korlan, Lee, Sungsik, Fan, Donghua, and Huang, Jier. Fri . "Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation". United States. https://doi.org/10.1021/acs.jpcc.9b09634. https://www.osti.gov/servlets/purl/1595943.
@article{osti_1595943,
title = {Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation},
author = {Zhou, Yixuan and Hu, Wenhui and Yang, Sizhuo and Zhang, Yunbo and Nyakuchena, James and Duisenova, Korlan and Lee, Sungsik and Fan, Donghua and Huang, Jier},
abstractNote = {Metal organic frameworks (MOFs) have emerged as a novel platform offering new promise for photocatalytic applications. In this work, we report a mixed-node MOF (MOF-74) based on earth-abundant metals (i.e., Co and Fe) as highly active and robust photocatalysts for visible light-driven H2 generation. Using in situ X-ray absorption spectroscopy which allows us to selectively probe the individual metal node in MOFs, we unambiguously identified the catalytic active sites and captured the key intermediate species under the standard catalytic conditions. We show that both Co and Fe centers in MOF-74 are the reversible active sites, and the accumulation of their reduced states is responsible for the observed induction period for H2 generation. Moreover, we captured the key intermediate species formed when the reaction reaches equilibrium, which is featured by an elongated Co–O bond at the Co center and a more distorted octahedral geometry at the Fe center with respect to their original geometry. These results not only demonstrate the potential of MOF-74 as a single site catalyst for H2 generation but also provide new insight into the catalytic mechanism for further development.},
doi = {10.1021/acs.jpcc.9b09634},
journal = {Journal of Physical Chemistry. C},
number = 2,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Save / Share:

Works referenced in this record:

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Reticular synthesis and the design of new materials
journal, June 2003

  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

Applications for Metal−Organic Frameworks (MOFs) as Quantum Dot Semiconductors
journal, January 2007

  • Llabrés i. Xamena, Francesc X.; Corma, Avelino; Garcia, Hermenegildo
  • The Journal of Physical Chemistry C, Vol. 111, Issue 1
  • DOI: 10.1021/jp063600e

Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts
journal, August 2012

  • Feng, Dawei; Gu, Zhi-Yuan; Li, Jian-Rong
  • Angewandte Chemie International Edition, Vol. 51, Issue 41
  • DOI: 10.1002/anie.201204475

Zr-based metal–organic frameworks: design, synthesis, structure, and applications
journal, January 2016

  • Bai, Yan; Dou, Yibo; Xie, Lin-Hua
  • Chemical Society Reviews, Vol. 45, Issue 8
  • DOI: 10.1039/c5cs00837a

Photocatalytic Carbon Dioxide Reduction with Rhodium-based Catalysts in Solution and Heterogenized within Metal-Organic Frameworks
journal, January 2015


Metal–Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
journal, February 2016

  • Zhang, Teng; Manna, Kuntal; Lin, Wenbin
  • Journal of the American Chemical Society, Vol. 138, Issue 9
  • DOI: 10.1021/jacs.6b00849

A metal–organic framework immobilised iridium pincer complex
journal, January 2016

  • Rimoldi, Martino; Nakamura, Akitake; Vermeulen, Nicolaas A.
  • Chemical Science, Vol. 7, Issue 8
  • DOI: 10.1039/c6sc01376g

Self-Healing of Molecular Catalyst and Photosensitizer on Metal–Organic Framework: Robust Molecular System for Photocatalytic H 2 Evolution from Water
journal, July 2016

  • Kim, Dongha; Whang, Dong Ryeol; Park, Soo Young
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04552

Evidence of Photoinduced Charge Separation in the Metal-Organic Framework MIL-125(Ti)-NH 2
journal, August 2012

  • de Miguel, Maykel; Ragon, Florence; Devic, Thomas
  • ChemPhysChem, Vol. 13, Issue 16
  • DOI: 10.1002/cphc.201200411

Delayed electron–hole pair recombination in iron( iii )-oxo metal–organic frameworks
journal, January 2014

  • Laurier, Katrien G. M.; Fron, Eduard; Atienzar, Pedro
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 11
  • DOI: 10.1039/c3cp55028a

A Water-Stable Porphyrin-Based Metal-Organic Framework Active for Visible-Light Photocatalysis
journal, June 2012

  • Fateeva, Alexandra; Chater, Philip A.; Ireland, Christopher P.
  • Angewandte Chemie International Edition, Vol. 51, Issue 30
  • DOI: 10.1002/anie.201202471

Photochemical Hydrogen Production with Metal–Organic Frameworks
journal, August 2016


Solvent-assisted linker exchange (SALE) and post-assembly metallation in porphyrinic metal–organic framework materials
journal, January 2013

  • Takaishi, Shinya; DeMarco, Erica J.; Pellin, Michael J.
  • Chemical Science, Vol. 4, Issue 4, p. 1509-1513
  • DOI: 10.1039/c2sc21516k

A Bioinspired Synthetic Approach for Building Metal−Organic Frameworks with Accessible Metal Centers
journal, November 2010

  • Barron, Paul M.; Wray, Curtis A.; Hu, Chunhua
  • Inorganic Chemistry, Vol. 49, Issue 22
  • DOI: 10.1021/ic101459j

Light-Harvesting Metal–Organic Frameworks (MOFs) Efficient Strut-to-Strut Energy Transfer in Bodipy and Porphyrin-Based MOFs
journal, October 2011

  • Lee, Chang Yeon; Farha, Omar K.; Hong, Bong Jin
  • Journal of the American Chemical Society, Vol. 133, Issue 40, p. 15858-15861
  • DOI: 10.1021/ja206029a

Visible-Light Photoreduction of CO 2 in a Metal–Organic Framework: Boosting Electron–Hole Separation via Electron Trap States
journal, October 2015

  • Xu, Hai-Qun; Hu, Jiahua; Wang, Dengke
  • Journal of the American Chemical Society, Vol. 137, Issue 42
  • DOI: 10.1021/jacs.5b08773

Elucidating Charge Separation Dynamics in a Hybrid Metal–Organic Framework Photocatalyst for Light-Driven H 2 Evolution
journal, February 2018

  • Yang, Sizhuo; Fan, Donghua; Hu, Wenhui
  • The Journal of Physical Chemistry C, Vol. 122, Issue 6
  • DOI: 10.1021/acs.jpcc.8b00471

Real-Time Visualization of Active Species in a Single-Site Metal–Organic Framework Photocatalyst
journal, February 2018


Photocatalytic CO 2 Reduction to Formate Using a Mn(I) Molecular Catalyst in a Robust Metal–Organic Framework
journal, July 2015


Two-Dimensional Metal–Organic Surfaces for Efficient Hydrogen Evolution from Water
journal, December 2014

  • Clough, Andrew J.; Yoo, Joseph W.; Mecklenburg, Matthew H.
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja5116937

Immobilizing Molecular Metal Dithiolene-Diamine Complexes on 2D Metal-Organic Frameworks for Electrocatalytic H 2 Production
journal, December 2016

  • Dong, Renhao; Zheng, Zhikun; Tranca, Diana C.
  • Chemistry - A European Journal, Vol. 23, Issue 10
  • DOI: 10.1002/chem.201605337

Enhanced Photochemical Hydrogen Production by a Molecular Diiron Catalyst Incorporated into a Metal–Organic Framework
journal, October 2013

  • Pullen, Sonja; Fei, Honghan; Orthaber, Andreas
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja407176p

Iron(III)-Based Metal–Organic Frameworks As Visible Light Photocatalysts
journal, September 2013

  • Laurier, Katrien G. M.; Vermoortele, Frederik; Ameloot, Rob
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja405086e

Mixed-Node Metal–Organic Frameworks as Efficient Electrocatalysts for Oxygen Evolution Reaction
journal, September 2018


In situ growth of well-ordered NiFe-MOF-74 on Ni foam by Fe 2+ induction as an efficient and stable electrocatalyst for water oxidation
journal, January 2018

  • Xing, Jiale; Guo, Kailu; Zou, Zehua
  • Chemical Communications, Vol. 54, Issue 51
  • DOI: 10.1039/c8cc03112f

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74
journal, November 2014

  • Tan, Kui; Zuluaga, Sebastian; Gong, Qihan
  • Chemistry of Materials, Vol. 26, Issue 23
  • DOI: 10.1021/cm5038183

Adsorption Sites and Binding Nature of CO 2 in Prototypical Metal−Organic Frameworks: A Combined Neutron Diffraction and First-Principles Study
journal, June 2010

  • Wu, Hui; Simmons, Jason M.; Srinivas, Gadipelli
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 13
  • DOI: 10.1021/jz100558r

Understanding Structure, Metal Distribution, and Water Adsorption in Mixed-Metal MOF-74
journal, December 2016

  • Howe, Joshua D.; Morelock, Cody R.; Jiao, Yang
  • The Journal of Physical Chemistry C, Vol. 121, Issue 1
  • DOI: 10.1021/acs.jpcc.6b11719

Constructing NiCo/Fe 3 O 4 Heteroparticles within MOF-74 for Efficient Oxygen Evolution Reactions
journal, October 2018

  • Wang, Xiaolu; Xiao, Hai; Li, Ang
  • Journal of the American Chemical Society, Vol. 140, Issue 45
  • DOI: 10.1021/jacs.8b08744

Synthesis, Fine Structural Characterization, and CO 2 Adsorption Capacity of Metal Organic Frameworks-74
journal, April 2014

  • Adhikari, Abhijit Krishna; Lin, Kuen-Song
  • Journal of Nanoscience and Nanotechnology, Vol. 14, Issue 4
  • DOI: 10.1166/jnn.2014.8621

Investigation of Acid Sites in a Zeotypic Giant Pores Chromium(III) Carboxylate
journal, March 2006

  • Vimont, Alexandre; Goupil, Jean-Michel; Lavalley, Jean-Claude
  • Journal of the American Chemical Society, Vol. 128, Issue 10
  • DOI: 10.1021/ja056906s

Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application
journal, November 2017


Highly efficient and selective photocatalytic hydrogenation of functionalized nitrobenzenes
journal, January 2014

  • Yang, Xiu-Jie; Chen, Bin; Zheng, Li-Qiang
  • Green Chem., Vol. 16, Issue 3
  • DOI: 10.1039/c3gc42042f

Mechanism of Photocatalytic Hydrogen Generation by a Polypyridyl-Based Cobalt Catalyst in Aqueous Solution
journal, December 2014

  • Rodenberg, Alexander; Orazietti, Margherita; Probst, Benjamin
  • Inorganic Chemistry, Vol. 54, Issue 2
  • DOI: 10.1021/ic502591a

Photoactive Zeolitic Imidazolate Framework as Intrinsic Heterogeneous Catalysts for Light-Driven Hydrogen Generation
journal, December 2016


Exceptionally Robust CuInS 2 /ZnS Nanoparticles as Single Component Photocatalysts for H 2 Evolution
journal, August 2017

  • Zhou, Yulu; Hu, Wenhui; Ludwig, John
  • The Journal of Physical Chemistry C, Vol. 121, Issue 35
  • DOI: 10.1021/acs.jpcc.7b05241

Hydrogen Evolution Catalyzed by Cobaloximes
journal, December 2009

  • Dempsey, Jillian L.; Brunschwig, Bruce S.; Winkler, Jay R.
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar900253e

Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: Recent progress and future challenges
journal, January 2012

  • Du, Pingwu; Eisenberg, Richard
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee03250c

Light-Driven Hydrogen Generation: Efficient Iron-Based Water Reduction Catalysts
journal, December 2009

  • Gärtner, Felix; Sundararaju, Basker; Surkus, Annette-Enrica
  • Angewandte Chemie International Edition, Vol. 48, Issue 52
  • DOI: 10.1002/anie.200905115

A dye-sensitized Pt@UiO-66(Zr) metal–organic framework for visible-light photocatalytic hydrogen production
journal, January 2014

  • He, Jiao; Wang, Jiaqiang; Chen, Yongjuan
  • Chem. Commun., Vol. 50, Issue 53
  • DOI: 10.1039/c4cc01086h

Stable and improved visible-light photocatalytic hydrogen evolution using copper( ii )–organic frameworks: engineering the crystal structures
journal, January 2017

  • Song, Ting; Zhang, Li; Zhang, Piyong
  • Journal of Materials Chemistry A, Vol. 5, Issue 13
  • DOI: 10.1039/c7ta00095b

Visible Light-Driven Hydrogen Production from Aqueous Protons Catalyzed by Molecular Cobaloxime Catalysts
journal, June 2009

  • Du, Pingwu; Schneider, Jacob; Luo, Genggeng
  • Inorganic Chemistry, Vol. 48, Issue 11
  • DOI: 10.1021/ic900389z

A Homogeneous System for the Photogeneration of Hydrogen from Water Based on a Platinum(II) Terpyridyl Acetylide Chromophore and a Molecular Cobalt Catalyst
journal, September 2008

  • Du, Pingwu; Knowles, Kathryn; Eisenberg, Richard
  • Journal of the American Chemical Society, Vol. 130, Issue 38
  • DOI: 10.1021/ja804650g